US5399429A - Flame retardant recycled polyester copolymers - Google Patents
Flame retardant recycled polyester copolymers Download PDFInfo
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- US5399429A US5399429A US08/209,937 US20993794A US5399429A US 5399429 A US5399429 A US 5399429A US 20993794 A US20993794 A US 20993794A US 5399429 A US5399429 A US 5399429A
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- Prior art keywords
- phosphinic acid
- flame retardant
- carboxyethyl
- polyester
- linear polyester
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Definitions
- This invention relates to new flame retardant polyester compositions. More particularly, this invention relates to new flame retardant copolyesters produced from recycled polyesters and to a method for producing the copolyester compositions. More particularly this invention relates to new flame retardant copolyesters produced from recycled polyethylene terephthalate, another dicarboxylate moiety and carboxy-phosphinic acids, a process for producing the copolyesters and shaped articles produced from the copolyesters.
- polyethylene terephthalate One of the major uses of polyethylene terephthalate is the production of bottles for milk and soft drinks and several billion bottles are produced for these uses each year. In recent years the environment has received greater attention and organized efforts have appeared to promote the recycling of many materials including the bottles made of polyethylene terephthalate to remove them from the growing volume of solid waste.
- Recycled polyethylene terephthalate can be processed into lower grade polyester products; however, the properties of recycled polyethylene terephthalate such as, for example, the glass transition temperature have generally been inferior when compared to the properties of virgin polyethylene terephthalate because the intrinsic viscosity is lower.
- Recycled polyethylene terephthalate has, thus, generally not been used for the production of products such as bottles or fibers where these properties are relatively critical. Instead the recycled polyethylene terephthalate, like other recycled plastic, has been used to produce products with less demanding requirements such as, for example, fibers for pillows, building materials such as plastic lumber and dividers for parking lots.
- polyesters One of the major uses of polyesters is the production of shaped polyester articles and of woven and non-woven textiles such as fabrics, filaments, staples or yarn and of sheets. In recent years efforts to make textiles less flammable, to improve the safety characteristics of products such as apparel, bedding, home furnishings, aircraft and automobile interior fabrics and industrial fabrics, have increased. It is also recognized that the textiles may be blends, particularly blends of natural fibers, such as cotton, and synthetic fibers, such as polyesters.
- U.S. Pat. No. 4,034,141 teaches the use of brominated phosphoramidates to treat combustible materials such as cotton and synthetic fibers to impart fire retardant properties.
- the fire retardant composition is applied by treating the fabric with a solution of the composition, drying the fabric and curing the composition.
- U.S. Pat. No. 3,969,437 teaches the use of a specific class of cyclic phosphorus esters to prepare a durable, flame retardant textile finish for cotton-polyester blends.
- the phosphorus ester used must contain at least one carbon-bonded primary alcohol group, and preferably two or more, plus a pentavalent phosphorus ester group.
- U.S. Pat. No. 3,922,323 teaches a process for improving the flame resistance of polyesters, especially unsaturated polyesters, by chemically binding and/or admixing organic phosphorus compounds and, if desired, halogen compounds into the polyesters.
- Halogen containing, at least bicyclic phosphonic esters which are free from hydroxy and carboxylic groups are used.
- U.S. Pat. No. 3,941,752 teaches a flame retarded, synthetic linear polyester modified with carboxy-phosphinic acids.
- the linear polyester is the polycondensation product of a dicarboxylic acid, a diol and a flame-retarding carboxy-phosphinic acid monomer which may contain hetero atoms.
- the need for a high value use for recycled polyester materials has grown.
- this invention is directed to copolyesters of a recycled polyester, a bis-hydroxy alkyl dicarboxylate and a carboxy-phosphinic acid monomer which have a flame retardant property and which have an intrinsic viscosity greater than about 0.6, and preferably within a range of from about 0.6 to about 1.2, and a glass transition temperature greater than about 65° C.
- the recycled polyester is preferably polyethylene terephthalate
- the bis-hydroxy alkyl dicarboxylate is preferably bis- ⁇ -hydroxy ethyl bibenzoate or bis- ⁇ -hydroxy ethyl naphthanate
- the carboxy-phosphinic acid monomer is preferably 2-carboxyethyl(phenyl) phosphinic acid, or the cyclic anhydride thereof.
- the bibenzoate, or the naphthanate is copolymerized along with the carboxy-phosphinic acid and recycled polyethylene terephthalate.
- the copolyester is preferably a polyethylene dicarboxylate copolyester having from 0% to about 99.9% by weight of recycled polyethylene terephthalate, from 0% to about 99.9% by weight of bis-hydroxy alkyl bibenzoate and from about 0.1% to about 10% by weight of the carboxy-phosphinic acid monomer.
- the copolyester is produced by placing the desired amounts of recycled polyethylene terephthalate, hydroxy alkyl bibenzoate and carboxy-phosphinic acid in a nitrogen filled reactor in the presence of a catalyst which is preferably based upon antimony such as, for example, antimony oxide. The reactor is heated to a temperature within the range of from about 250° C.
- a vacuum is applied slowly to reduce the pressure to a pressure within the range of from about 0.5 to about 1.0 mm of mercury.
- copolyesters of polyethylene terephthalate also includes copolyesters of other polyalkylene dicarboxylates such as polybutylene terephthalate and polyethylene naphthanate.
- the present invention relates to copolyesters of recycled polyesters having flame retardant properties.
- the copolyesters of this invention have an intrinsic viscosity greater than about 0.6, and preferably within the range of from about 0.6 to about 1.2.
- the copolyesters of recycled polyethylene terephthalate are preferably a polyethylene dicarboxylate copolyester having from 0% to about 99.9% by weight recycled polyethylene terephthalate, from 0% to about 99.9% by weight of another dicarboxylate moiety, which is preferably a bis-hydroxy alkyl bibenzoate and more preferably bis- ⁇ -hydroxy ethyl bibenzoate, and from about 0.1% to about 10% by weight of a flame retarding carboxy-phosphinic acid monomer having the general formula: ##STR1## wherein R is a saturated open-chain or cyclic alkylene radical having from one to about 15 carbon atoms, preferably from 2 to about 10 carbon atoms, or an arylene or
- the carboxy-phosphinic acid is preferably 2-carboxyethyl(phenyl) phosphinic acid, 2-carboxyethyl(methyl) phosphinic acid, the cyclic anhydride of 2-carboxyethyl(phenyl) phosphinic acid or the cyclic anhydride of 2-carboxyethyl(methyl) phosphinic acid.
- Polymerization of 90% by weight recycled polyethylene terephthalate and 10% by weight 2-carboxyethyl(phenyl)phosphinic acid produced a flame retardant polyester having an intrinsic viscosity of about 0.70.
- the polyester had a slight drop in the glass transition temperature, the melting point and the crystallinity when compared to virgin polyethylene terephthalate, but the color of the polyester was improved.
- the glass transition temperature, melting point and crystallinity of the polyester produced from recycled polyethylene terephthalate is improved by the addition of another dicarboxylate moiety in accordance with this invention.
- recycled polyethylene terephthalate is the preferred recycled polyester
- other polyalkylene terephthalates such as, for example, polybutylene terephthalate can be used.
- Other polyalkylene dicarboxylates such as, for example polyethylene or polybutylene naphthanate can also be used.
- the dicarboxylate moiety can be produced from any dicarboxylic acid except unsubstituted terephthalic acid.
- the dicarboxylate moiety can be produced from an aliphatic group having from 2 to about 12 carbon atoms, from substituted or unsubstituted isophthalic acid, from the substituted or unsubstituted dicarboxylic acids of biphenyls, naphthalene, terphenyls and other polyaromatics such as, for example, diphenyl ether, and from substituted terephthalic acid.
- the copolyesters of this invention are produced.
- the dicarboxylate moiety is preferably an aromatic bis-hydroxy alkyl dicarboxylate.
- the dicarboxylate moiety is a hydroxy ethyl dicarboxylate compound or other hydroxy alkyl dicarboxylate compound having the general formula:
- R is selected from the group consisting of aliphatic groups having from 2 to about 12 carbon atoms; substituted benzene wherein the substituent is a halogen, an alkyl group having a carbon chain of from 1 to about 8 carbon atoms, or a substituted or unsubstituted phenyl group; naphthyl and substituted naphthyl wherein the substituent is hydrogen, halogen, an alkyl group having a carbon chain having from 1 to about 8 carbon atoms, or phenyl and substituted phenyl; and a moiety having the general formula:
- R 1 is selected from the group consisting of nil, oxygen, phenyl and substituted phenyl, an alkyl group having a carbon chain of from 1 to about 8 carbon atoms, and --HC ⁇ CH--; and wherein each R 2 is independently selected from the group consisting of hydrogen, halogen, an alkyl group having a carbon chain having from 1 to about 8 carbon atoms, phenyl and substituted phenyl. More specifically the dicarboxylate moiety is preferably produced from bis- ⁇ -hydroxy ethyl bibenzoate.
- dicarboxylate moiety is preferably a hydroxy ethyl dicarboxylate compound
- other hydroxy alkyl groups may be used and it is preferred that each of the alkyl groups be independently selected from the group consisting of alkyl radicals having from 1 to 8 carbon atoms such as, for example, methyl, propyl, isopropyl, butyl, hexyl, 2-ethylbutyl, octyl and 2-ethylhexyl groups.
- the preferred dicarboxylate monomer is bis- ⁇ -hydroxy ethyl bibenzoate; however, the biphenyl moiety is not required.
- the copolyesters of this invention may be produced equally well from a naphthanate or another dicarboxylate such as, for example, bis-hydroxy ethyl naphthanate, bis-hydroxy ethyl isophthalate, and bis-hydroxy ethyl diphenyl ether.
- these examples are of dicarboxylates having bis-hydroxy ethyl groups, other hydroxy alkyls such as, for example, bis-hydroxy butyl, bis-hydroxy hexyl and bis-hydroxy octyl groups can be used.
- the dicarboxylate moieties used in the process have structures which will strengthen the polymer and impart rigidity to the polymer backbone. As a result the copolyester will have a higher glass transition temperature and the tensile and flexural properties of the polyester will be improved.
- the resulting copolyester of recycled polyethylene terephthalate and the dicarboxylic moiety has an increased molecular weight, both weight average molecular weight (Mw) and number average molecular weight (Mn), when compared to the molecular weight of virgin polyethylene terephthalate without the inclusion of the dicarboxylate moiety of this invention.
- copolyesters When polyethylene naphthanate or other dicarboxylates are used to produce copolyesters in accordance with this invention, the resulting copolyesters have improved performance characteristics or properties such as, for example, increased intrinsic viscosity and higher glass transition temperature.
- the improvement in the characteristics of copolyesters produced from naphthanates or other dicarboxylates is similar to the improvement in the characteristics of recycled polyethylene terephthalate when it is used in accordance with this invention.
- the lower molecular weight of the polyester produced from recycled polyethylene terephthalate without the inclusion of the dicarboxylate moiety is believed to be caused by chain scission, the breaking of carbon-carbon bonds, during the recycling process.
- the inclusion of the dicarboxylate moiety and the carboxy-phosphinic acid in the process of this invention promotes chain bonding to produce longer carbon chains and, thus, higher molecular weights.
- the inclusion of the dicarboxylic moiety and the carboxy phosphinic acid is a complex process in which the intrinsic viscosity of the process fluid drops originally from the viscosity of the polyethylene terephthalate to as low as about 0.25 before it begins to rise and the intrinsic viscosity of the copolyester may reach as high as about 1.2 if the process is allowed to go to completion.
- the flame retarding carboxy-phosphinic acid monomer having the general formula: ##STR2## wherein R is a saturated open-chain or cyclic alkylene radical having from one to about 15 carbon atoms, preferably from 2 to about 10 carbon atoms, or an arylene or aralkylene radical having from 1 to about 15 carbon atoms such as, for example, methyl, ethyl, propyl, isopropyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, iso-octyl, decyl, isodecyl, dodecyl, tetradecyl, --C 6 H 4 --, --C 6 H 4 --CH 2 --, and --C 6 H 4 --CH 2 --CH 2 --, and R 1 is an alkyl radical having up to about 6 carbon atoms, an aryl radical or an alkaryl radical wherein
- the carboxy-phosphinic acid is preferably 2-carboxyethyl(phenyl) phosphinic acid, 2-carboxyethyl(methyl) phosphinic acid, the cyclic anhydride of 2-carboxyethyl(phenyl) phosphinic acid or the cyclic anhydride of 2-carboxyethyl(methyl) phosphinic acid.
- the preferred acid, 2-carboxyethyl (phenyl)phosphinic acid may be prepared in accordance with the teaching in U.S. Pat. No. 4,081,463.
- the 2-carboxyethyl(phenyl)phosphinic acid is prepared in two stages by first reacting dichloro(phenyl)phosphine with acrylic acid employed at a molar excess of 25% to 45% to form a mixture of three intermediates, 3-(chlorophenylphosphinyl) propionyl chloride, the cyclic anhydride of 2-carboxyethyl(phenyl)phosphinic acid and the mixed anhydride of acrylic acid with 3-chlorocarbonyl-ethyl(phenyl)phosphinic acid.
- the second stage of the process is the hydrolysis of the of the mixture of the three intermediates to obtain the desired product, 2-carboxyethyl(phenyl)phosphinic acid.
- the flame retardant copolyesters of recycled polyethylene terephthalate are preferably polyethylene dicarboxylate copolyesters having from about 99.9% to 0% by weight recycled polyethylene terephthalate, from 0% to about 99.9% by weight of another dicarboxylate moiety and from about 0.1% to about 10% of the flame retarding 2-carboxyethyl(phenyl)phosphinic acid, or the cyclic anhydride thereof.
- the properties desired in the copolyester products will determine the amount of the other dicarboxylate moiety included in the copolyester.
- the desired polyester of this invention may be produced by the polymerization of from about 99.9% to about 90% by weight recycled polyethylene terephthalate and from about 0.1% to about 10% by weight of 2-carboxyethyl(phenyl) phosphinic acid
- the properties of the polyester can be improved by the addition of a hydroxy ethyl bibenzoate, preferably bis- ⁇ -hydroxy ethyl bibenzoate, to the polymerization to produce a copolyester.
- a hydroxy ethyl bibenzoate preferably bis- ⁇ -hydroxy ethyl bibenzoate
- Copolyesters of recycled polyethylene terephthalate having from about 0.1% to about 20% of another dicarboxylate moiety, such as a bibenzoate or naphthanate produce a polyester that has a low melting point (Tm), low crystallinity and a low rate of crystallization.
- Tm melting point
- these copolyesters have a higher glass transition temperature and better stability against ultraviolet light than polyethylene terephthalate.
- These polyesters would be particularly suited for use in the production of biaxially oriented films or other similar products.
- a large portion of the production of polyethylene terephthalate is based upon the melt polymerization of terephthalic acid and ethylene glycol.
- the melt polymerization process produces polyethylene terephthalate having an inherent viscosity of about 0.6 and it is necessary to use solid state polymerization in addition to the melt polymerization to raise the inherent viscosity of the polyethylene terephthalate to the range of 0.9 to 1.2 that is needed for the production of many products.
- copolymers of recycled polyethylene terephthalate and another dicarboxylate wherein the copolyesters have about 99.9% by weight recycled polyethylene terephthalate and wherein the copolyesters have about 99.9% by weight of the other dicarboxylate moiety.
- copolyesters of polyethylene terephthalate are dependent upon the amount of the other dicarboxylate moiety included in the copolyester.
- Copolyesters having from about 99.9% to about 80% by weight polyethylene terephthalate and from about 0.1% to about 20% by weight of another dicarboxylate moiety have a low melting point, low crystallinity and a higher glass transition temperature.
- Copolyesters having from about 80% to about 55% by weight polyethylene terephthalate and from about 20% to about 45% by weight of another dicarboxylate moiety are amorphous.
- Copolyesters having from about 55% to about 10% by weight polyethylene terephthalate and from about 45% to about 90% by weight of another dicarboxylate moiety have a high melting point, high crystallinity and a higher glass transition temperature.
- the copolyesters were produced by placing the desired amounts of polyethylene terephthalate, bis- ⁇ -hydroxy ethyl bibenzoate and 2-carboxyethyl(phenyl)phosphinic acid in a nitrogen filled reactor in the presence of a catalyst which is preferably antimony oxide.
- the reactor was heated to a temperature within a range of from about 250° C. to about 293° C., and preferably within a range of from about 263° C. to about 293° C., for about 3 hours.
- a vacuum was applied slowly to reduce the pressure to a pressure of from about 0.5 to about 1.0 mm of mercury. The reaction was continued at those conditions for an additional 0.5 to 1.5 hours and the heat and vacuum were then removed.
- copolyesters and processes have been described above using polyethylene terephthalate and the preferred hydroxy ethyl dicarboxylate moiety.
- the copolyesters can also be produced by using ethylene glycol and the appropriate diacid in the process with the polyethylene terephthalate.
- ethylene glycol and biphenyl dicarboxylic acid may be used in the process to replace bis- ⁇ -hydroxy ethyl bibenzoate,
- ethylene glycol and naphthalene dicarboxylic acid may be used.
- Ethylene glycol was used in the above description of the process and it is the preferred diol.
- other aliphatic diols such as, for example, aliphatic diols having from 3 to about 7 carbon atoms, may also be used.
- the carboxy-phosphinic acid and its cyclic anhydride are not volatile under the process conditions for production of the polyesters so they can be incorporated in the polyester by inclusion in the condensation reaction. When incorporated into the molecule during the condensation reaction the phosphorus containing structural unit is randomly distributed in the linear polyester product.
- the polyesters of this invention may be made into shaped articles. They may be spun into filaments and fibers using well known processes and the standard additional treatments. The polyesters may also be extruded into sheets or formed into shaped articles which may be solid or hollow by press molding, injection molding and extrusion. All of these shaped articles (fibers, sheets and other shapes) are also an object of this invention.
- the fibers and filaments have very good and permanent flame retardant and self-extinguishing properties. Since they have a good degree of whiteness, they have very good dyeing properties for disperse dyestuffs and their receptivity includes acid dyestuffs in color shades of average to deep intensity.
- the tensile strength of the filaments and fibers, second order transition temperature and melting point approximately correspond to the values for polyesters which do not contain the flame retardant carboxy-phosphinic acid.
- the fibers and filaments are generally useful for applications where readily ignitible textiles cannot be tolerated and it is possible to use these fibers in combination with natural fibers, such as cotton, and other synthetic fibers.
- Sheets and shaped articles produced from the flame retardant polyester are generally used in locations where it is desired to reduce the possible serious risks if ignition and a fire occur. If the transparency of the shaped articles is not of concern, their solidity and flame retarding properties can be enhanced by the inclusion of inorganic fiber materials such as, for example, glass and quartz fibers and carbon in the usual quantities, in the polyester before molding.
- a polyethylene terephthalate bottle such as those which contain soft drinks, was washed with detergent and water, cut into pieces and dried at a temperature of about 60° C. for 7 hours in a vacuum oven.
- the flask was evacuated and filled with nitrogen 3 times at room temperature and then a continuous, slow flow of nitrogen was maintained through the flask.
- the flask was placed in a salt bath which had been preheated to about 250° C.
- the temperature of the salt bath was raised from 250° C. to about 285° C. over a period of 1 hour and ethylene glycol was distilled off.
- the pressure was then reduced to 150 millitorr over a period of about 1 hour.
- the pressure in the flask was further reduced to about 50 millitorr over a period of about 30 minutes and the reaction was continued at these conditions for an additional 45 minutes at which time the heat and vacuum were removed.
- the resulting copolymer had an intrinsic viscosity of 0.79 at a concentration of 0.5 grams/deciliter in a solution of 60% phenol/40% tetrachloroethane at 25° C.
- the glass transition temperature was determined to be 70° C. by differential scanning calorimeter. This example is shown as Example 4 in the Table below.
- the reaction of this Example was repeated 4 times and the ratio between the reactants, the ratio of the recycled polyethylene terephthalate to the bis- ⁇ -hydroxy ethyl bibenzoate and carboxy-phosphinic acid was varied in accordance with this invention.
- the reaction was repeated with only polyethylene terephthalate and with polyethylene terephthalate and bis- ⁇ -hydroxy ethyl bibenzoate.
- the reaction was also repeated changing the ratio between the polyethylene terephthalate and the bis- ⁇ -hydroxy ethyl bibenzoate while maintaining a constant amount of the carboxy-phosphinic acid. Examples 1-4 are shown in the Table below.
- Examples 1-4 The reaction of Examples 1-4 was modified to illustrate another embodiment of the invention.
- the bis- ⁇ -hydroxy ethyl bibenzoate was replaced by biphenyl dicarboxylic acid and ethylene glycol.
- 16 grams of recycled polyethylene terephthalate (PET) 2 grams of 4,4'-biphenyl dicarboxylic acid (BDA), 2 grams of 2-carboxyethyl(phenyl) phosphinic acid (CPA) and 3.5 grams of ethylene glycol (EG) were reacted in the presence of 0.004 grams of antimony oxide.
- PET polyethylene terephthalate
- BDA 4,4'-biphenyl dicarboxylic acid
- CPA 2-carboxyethyl(phenyl) phosphinic acid
- EG ethylene glycol
- the resulting copolymer had an intrinsic viscosity of 0.77 at a concentration of 0.5 grams/deciliter in a solution of 60% phenol/40% tetrachloroethane at 25° C.
- the glass transition temperature was determined to be 70° C. by differential scanning calorimeter.
- Example 5 is shown in the Table below.
- Examples 1-4 The reaction of Examples 1-4 was modified to illustrate another embodiment of the invention.
- the bis- ⁇ -hydroxy ethyl bibenzoate was replaced by naphthalene dicarboxylic acid and ethylene glycol.
- 16 grams of recycled polyethylene terephthalate (PET) 2 grams of 2,6-naphthalene dicarboxylic acid (NDA), 2 grams of 2-carboxyethyl(phenyl) phosphinic acid (CPA) and 3.5 grams of ethylene glycol (EG) were reacted in the presence of 0.004 grams of antimony oxide.
- PET polyethylene terephthalate
- NDA 2,6-naphthalene dicarboxylic acid
- CPA 2-carboxyethyl(phenyl) phosphinic acid
- EG ethylene glycol
- the resulting copolymer had an intrinsic viscosity of 0.77 at a concentration of 0.5 grams/deciliter in a solution of 60% phenol/40% tetrachloroethane at 25° C.
- the glass transition temperature was determined to be 70° C. by differential scanning calorimeter.
- Example 6 is shown in the Table below.
- the following Table shows the results of the reactions described in the Examples above.
- the Table includes the ratio of the reactants, the amount of the catalyst (antimony oxide) present in the reactor during the reaction and properties of the resulting copolymers.
- the properties included in the Table are the intrinsic viscosity (I.V.), the molecular weight as weight average molecular weight (Mw) and number average molecular weight (Mn), and the glass transition temperature in degrees Centigrade (Tg). The melting point in degrees Centigrade is also shown for Example 4.
Abstract
Description
HO--(CH.sub.2).sub.n --O--CO--R--CO--O--(CH.sub.2).sub.n --OH
--(C.sub.6 H.sub.3 R.sup.2)--R.sup.1 --(C.sub.6 H.sub.3 R.sup.2)--
TABLE 1 ______________________________________ GRAMS EX- OF AM- RATIO CAT- Mw/ Tg(°C.)/ PLE PET/HEB/CPA/EG ALYST I.V. Mn MP(°C.) ______________________________________ 1 20/0/0/0 -- 0.7 4.67/ 82 (Con- 11.8 trol) 2 18/2/0/0 0.004 1.28 -- 85 (Con- trol) 3 16/2/2/3.2 0.004 0.79 -- 70 4 2/16/2/0 0.004 0.64 -- 91/245 5 PET/BDA/CPA/EG 0.004 0.70 -- 70 15/2/2/3.5 6 PET/NDA/CPA/EG 0.004 0.70 -- 70 16/2/2/3.5 ______________________________________
Claims (45)
HO--(CH.sub.2).sub.n --O--CO--R--CO--O--(CH.sub.2).sub.n --OH
--(C.sub.6 H.sub.3 R.sup.2)--R.sup.1 --(C.sub.6 H.sub.3 R.sup.2)--
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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US08/209,937 US5399429A (en) | 1994-03-11 | 1994-03-11 | Flame retardant recycled polyester copolymers |
TW084101874A TW281684B (en) | 1994-03-11 | 1995-03-01 | |
MX9603870A MX9603870A (en) | 1994-03-11 | 1995-03-03 | Flame-retardant recycled polyester copolymers. |
EP95912683A EP0749459A1 (en) | 1994-03-11 | 1995-03-03 | Flame-retardant recycled polyester copolymers |
KR1019960704885A KR970701756A (en) | 1994-03-11 | 1995-03-03 | Flame-retardant Recycled Polyester Copolymer (FLAME-RETARDANT RECYCLED POLYESTER COPOLYMERS) |
CA002183359A CA2183359A1 (en) | 1994-03-11 | 1995-03-03 | Flame-retardant recycled polyester copolymers |
PCT/US1995/002596 WO1995024446A1 (en) | 1994-03-11 | 1995-03-03 | Flame-retardant recycled polyester copolymers |
JP7523524A JPH09510244A (en) | 1994-03-11 | 1995-03-03 | Flame retardant recycled polyester copolymer |
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US08/209,937 US5399429A (en) | 1994-03-11 | 1994-03-11 | Flame retardant recycled polyester copolymers |
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US5399429A true US5399429A (en) | 1995-03-21 |
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US08/209,937 Expired - Lifetime US5399429A (en) | 1994-03-11 | 1994-03-11 | Flame retardant recycled polyester copolymers |
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US (1) | US5399429A (en) |
EP (1) | EP0749459A1 (en) |
JP (1) | JPH09510244A (en) |
KR (1) | KR970701756A (en) |
CA (1) | CA2183359A1 (en) |
MX (1) | MX9603870A (en) |
TW (1) | TW281684B (en) |
WO (1) | WO1995024446A1 (en) |
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US5658662A (en) * | 1993-12-27 | 1997-08-19 | Hoechst Aktiengesellschaft | High tenacity, low flammability polyester yarn, production thereof and use thereof |
US5468780A (en) * | 1994-06-21 | 1995-11-21 | Miyaso Chemical Co. | Method of recycling unsaturated polyester resin waste |
US6538054B1 (en) * | 1996-10-21 | 2003-03-25 | Basf Aktiengesellschaft | Flame-proof moulding compounds |
US6046265A (en) * | 1998-01-21 | 2000-04-04 | General Electric Company | Crystalline resin compositions having a special effect surface appearance |
US20070225414A1 (en) * | 2006-03-21 | 2007-09-27 | Clariant International Ltd | Phosphorus-containing mixtures, a process for their preparation and their use |
US8063123B2 (en) * | 2006-03-21 | 2011-11-22 | Clariant Finance (Bvi) Limited | Phosphorus-containing mixtures, a process for their preparation and their use |
US20070281158A1 (en) * | 2006-05-15 | 2007-12-06 | Glew Charles A | UV and flame resistant textile polymer yarn |
US10906226B2 (en) | 2010-05-06 | 2021-02-02 | Clariant Masterbatches (Italia) Spa | Process for the production of multilayer blow-molded hollow articles |
US9586384B2 (en) * | 2010-08-10 | 2017-03-07 | Essel Propack Ltd. | Multi-layer sheet and method thereof |
US20130136908A1 (en) * | 2010-08-10 | 2013-05-30 | Mrinal Kanti Banjerjee | Multi-layer sheet and method thereof |
US8604105B2 (en) | 2010-09-03 | 2013-12-10 | Eastman Chemical Company | Flame retardant copolyester compositions |
US8969443B2 (en) | 2010-09-03 | 2015-03-03 | Eastman Chemical Company | Flame retardant copolyester compositions |
CN110330770A (en) * | 2019-04-22 | 2019-10-15 | 苏州聚冠复合材料有限公司 | A kind of modified RPET material of recyclable PET and preparation process |
CN110330770B (en) * | 2019-04-22 | 2022-04-22 | 苏州聚冠复合材料有限公司 | Recyclable PET modified RPET material and preparation process thereof |
CN114634688A (en) * | 2022-04-26 | 2022-06-17 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
CN114634688B (en) * | 2022-04-26 | 2023-09-01 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JPH09510244A (en) | 1997-10-14 |
MX9603870A (en) | 1997-03-29 |
CA2183359A1 (en) | 1995-09-14 |
KR970701756A (en) | 1997-04-12 |
TW281684B (en) | 1996-07-21 |
WO1995024446A1 (en) | 1995-09-14 |
EP0749459A1 (en) | 1996-12-27 |
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